CN104474926B - A kind of preparation method of polyamide reverse osmose membrane - Google Patents
A kind of preparation method of polyamide reverse osmose membrane Download PDFInfo
- Publication number
- CN104474926B CN104474926B CN201410766709.2A CN201410766709A CN104474926B CN 104474926 B CN104474926 B CN 104474926B CN 201410766709 A CN201410766709 A CN 201410766709A CN 104474926 B CN104474926 B CN 104474926B
- Authority
- CN
- China
- Prior art keywords
- mpd
- preparation
- organic
- phenylene diamine
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation method of reverse osmosis membrane, more specifically relate to a kind of rinsing and process equipment with high desalinization, high-flux reverse osmosis membrane and preparation method thereof very easily. The present invention has the functional fine and close composite bed of one deck in porous polysulfone supporting layer, the m-phenylene diamine (MPD) aqueous solution that functional fine and close composite bed contains by use the buffer salt system that organic acid with one or more hydroxyls or its hydrate and organic base form, forms in the surface polycondensation of porous polysulfone supporting layer with the organic solvent solution of the pyromellitic trimethylsilyl chloride that contains a certain amount of additive. Advantage of the present invention is required rinsing treatment process gentleness, simple, efficient, and in rinsing caudacoria, the residual total amount of unreacted amine is low, easily realizes the industrialization polyamide reverse osmose membrane preparation method of preparation fast continuously.
Description
Technical field
The present invention relates to a kind of preparation method of reverse osmosis membrane, more specifically relate to a kind of rinsing and process very easilyEquipment with high desalinization, high-flux reverse osmosis membrane and preparation method thereof.
Background technology
Reverse osmosis membrane is the one of filter membrane, possess and can make hydrone see through, and the water such as ion, molecules of salt beyond impureThe impervious special nature of thing. Its membrane aperture size is less compared with the fenestra of NF membrane, milipore filter below 2 nanometers. Because of its toolThere are the outstanding advantages such as higher product water consumption compares, at desalinization, brackish water desalination, wastewater treatment, pharmaceuticals industry quilt extensivelyGeneral application. Along with increase and the economic development of world population, the requirement of water is also in quick increase, greenhouse effects of the earth etc. in additionFactor also produces larger impact to water circulation, and global water resources is not enough, and this problem is perplexing countries in the world, seawater just day by dayDesalination reverse osmosis membrane technology is also to solve the effective means of this global problem, and 2007 so far to manufacture square measure according to statisticsFor the application in desalinization of the reverse osmosis membrane in the benchmark whole world occupies the overwhelming majority.
In actual seawater desalination desalination process, because seawater stoste is constantly concentrated separation, the salinity in its stosteCan constantly rise, the osmotic pressure of its generation also can constantly rise thereupon, if according to can be calculated in desalting process, and seawaterOriginal liquid concentration rises to 2 times of its original concentration gradually, and the driving pressure applying needs nearly 6MPa left and right constantly to obtainAvailable fresh water. Therefore consider from producing water consumption aspect according to this feature of seawater desalination reverse osmosis film applied environment,How desalinization film, on the basis that ensures its desalting performance and higher permeant flux, further reduces its necessary drivingPressure is crucial. Consider from producing water quality stabilizing aspect, how desalinization film is at seawater certain and that constantly riseIn original liquid concentration interval, ensure that its stable desalting performance and higher permeant flux are crucial. To this, numerous both domestic and externalPerson is by blend nano inorganic particle, polysulfone supporting layer material in reverse osmosis membrane surface modification, counter-infiltration polyamide composite film layerA large amount of research and Science Explorations have been done in the aspects such as modification.
The people such as Li Chadefu Fu Bige use contains the poly-of carboxylic acid group and optional pendant hydroxyl group or amide moietiesCompound is processed reverse osmosis membrane, has improved salt rejection or the water flux density (publication CN1031482A) of reverse osmosis membrane
Tool is grown and is forever waited people to use the aqueous solution that contains the compound that comprises at least one iodine atom to process aramid layer, improvesThe boron removal efficiency of aramid layer, be 8 at pressure 800psi, 25 DEG C, pH, the NaCl of 32000ppm and the simulated seawater of 5ppm boronUnder solution testing condition, its NaCl removal efficiency is 99.6-99.8%, and permeant flux is 8.9-15.2gfd. (granted patent CN101053787B)
It is molten that people's uses such as Zheng Sheng spoon comprise the mixing that contains two or more solvents with different solubilities parameter valueThe solution coat of agent, to the surface of porous support layer, forms polysulfones layer, on described polysulfones layer, forms polyamide active layer. ItsUnder 25 DEG C, the flow velocity of 800psi, 4.5L/min, 32000ppmNaCl aqueous solution water inlet test condition, it is de-that film properties reaches NaClExcept rate is 97.1-98.4%, permeant flux 30.5-47.3gfd. And pore size, hole number to polysulfone supporting layer surface enteredGone explanation, hole total quantity is 12500-12907 (1.27um × 0.83um surface area), and diameter is greater than hole more than 40nmQuantity is 26-58 (1.27um × 0.83um surface area), and the ratio that diameter is greater than shared whole holes, hole more than 40nm is0.20-0.45% (1.27um × 0.83um surface area) (publication CN103648622A)
The conventional preparation method of reverse osmosis membrane is generally by propping up at nonwoven cloth material surface-coated porous polysulfones at presentSupport layer, is reacted and is generated polyamide reverse osmosis layer by interfacial polycondensation on porous polysulfone supporting layer surface. At polyamide reverse osmosisIn film preparation process, because of water m-phenylene diamine (MPD) solution at nonwoven, porous polysulfone supporting layer and polyamide reverse osmose membraneSurplus in layer is residual, need to carry out rinsing processing to prepared polyamide reverse osmose membrane, if the insufficient meeting of rinsing causes instituteThe reverse-osmosis membrane element product turning black and changing color of preparation is rotten, finally causes the significantly decline of membrane component properties of product. EspeciallyIn desalinization diaphragm and element manufacture process thereof, the use amount of the polynary amine substance such as m-phenylene diamine (MPD) is larger, more easily causesState flaw.
For counter-infiltration polyamide rinsing processing, generally adopt warm water's rinsing processing or the strong acid and strong base of 40-90 DEG C to floatWash processing. The obturation that easily causes the effective hole of polysulfone supporting layer is processed in warm water's rinsing, causes the reduction of film permeant flux, and it is rawProduce line operation energy consumption higher. Strong acid and strong base rinsing is processed and is had relatively high expectations to equipment is corrosion-resistant, to production line operation ambient influnenceGreatly, easily operating personnel's health is caused to larger injury.
Therefore, need to study one and there is equipment with high desalinization, high yield water flux performance, and rinsing in its manufacture processTreatment process gentleness, simple, efficient, in rinsing caudacoria, the residual total amount of unreacted amine is low, easily realizes industrialization preparation fast continuouslyPolyamide reverse osmose membrane preparation method.
Summary of the invention
The object of present disclosure is to provide a kind of rinsing processing, and equipment with high desalinization, high yield water flux gather very easilyAcid amides reverse osmosis membrane preparation method, and the polyamide reverse osmose membrane of being prepared by the method, described polyamide reverse osmose membrane toolWhen having higher salt rejection rate and permeant flux, the post rinse process warm in its preparation process and, simple, efficient, after rinsingIn film, the residual total amount of unreacted amine is less than 100ppm, easily realizes industrialization preparation fast continuously.
The present invention is realized by following technical proposals, and equipment with high desalinization, height very are easily processed in a kind of rinsingPermeant flux polyamide reverse osmose membrane preparation method, is characterized in that, this polyamide reverse osmose membrane be use contain be with one orThe m-phenylene diamine (MPD) aqueous phase solution of the buffer salt system that the organic acid of multiple hydroxyls or its hydrate and organic base form, and containsThe organic solvent solution of the pyromellitic trimethylsilyl chloride of a certain amount of additive, at porous polysulfone supporting layer material surface, gathers by interfaceClose preparation and obtain. With the organic acid of one or more hydroxyls, its structural formula is shown in formula 1.
Formula 1
A preparation method for polyamide reverse osmose membrane, is characterized in that, has one deck merit in porous polysulfone supporting layerThe fine and close composite bed of energy property, functional fine and close composite bed is to contain organic acid or its hydrate with one or more hydroxyls by useThe m-phenylene diamine (MPD) aqueous solution of the buffer salt system forming with organic base, with the pyromellitic trimethylsilyl chloride that contains a certain amount of additiveOrganic solvent solution forms in the surface polycondensation of porous polysulfone supporting layer;
Additive wherein refers to tbp, triphenylphosphine, aluminium isopropoxide, acetone, acetylacetone,2,4-pentanedione, acetylacetone,2,4-pentanedioneOne in aluminium, nickel acetylacetonate, acetylacetone,2,4-pentanedione ruthenium (III), ferric acetyl acetonade, chromium acetylacetonate or acetylacetone,2,4-pentanedione gallium or severalCombination more than kind, the mass percent of additive in pyromellitic trimethylsilyl chloride is 0.005-2%; Pyromellitic trimethylsilyl chloride is organicMass percent in solvent solution is 0.05-3.0%;
Described buffer salt system is mixing with the organic acid of one or more hydroxyls or its hydrate and organic baseSolution, wherein, the organic acid with one or more hydroxyls adopting is lactic acid, D-malic acid, L MALIC ACID, DL-appleA kind of or two kinds of above combinations in acid, citric acid, tartaric acid or its hydrate; The organic base adopting be triethylamine,The combination of one or two or more kinds in trimethylamine or diethylamine;
The organic solvent adopting is in isoparM, isoparH, isoparL, isoparE, isoparG or n-hexaneOne or two or more kinds combination;
Described porous polysulfones support membrane surface apertures mean value between 10-30nm, deviate≤1.8; PorousThe hole count of polysulfone supporting layer surface unit area is at 200-600/um2Between, and porous polysulfone supporting layer is surveyed at 0.1MPaUnder pressure testing power, its pure water flux is 100-300L/m2Between/h;
The mass percent of the described organic acid with one or more hydroxyls in the m-phenylene diamine (MPD) aqueous solution is 0.1-5%; It is better when mass percent is 1.5-2.5%;
The mass percent of described organic base in the m-phenylene diamine (MPD) aqueous solution is 0.1-5%; Mass percent is 1.1-Better 1.5% time;
The mass percent of the m-phenylene diamine (MPD) in the described m-phenylene diamine (MPD) aqueous solution is 0.1-7%.
As preferably, the porous polysulfones support membrane surface apertures mean value described in above-mentioned preparation method is at 20-25nmBetween, deviate≤1.3; The hole count of porous polysulfone supporting layer surface unit area is at 400-500/um2Between; And porousProperty polysulfone supporting layer is under 0.1MPa test pressure, and its pure water flux is 200-250L/m2Between/h, porous polysulfone supporting layerAnd nonwoven stack thickness is between 120-170um, and polyamide reverse osmosis composite bed thickness is between 80-250nm.
As preferably, described in above-mentioned preparation method contain organic acid with one or more hydroxyls or its hydrate withThe modulator approach of the m-phenylene diamine (MPD) aqueous solution of the buffer salt system that organic base forms is first will contain and be with one or more hydroxylsOrganic acid or its hydrate join in pure water, make it fully dissolve that to be modulated into pH be the acid solution between 1.9-2.5; ThenAdding the abundant hybrid modulation of corresponding organic base to become pH is the cushioning liquid between 2.0-6.0, finally adds m-phenylene diamine (MPD) fully mixedClose and be modulated into pH and formed by contain organic acid with one or more hydroxyls or its hydrate and organic base between 4.5-7.2The m-phenylene diamine (MPD) aqueous solution of buffer salt system.
As preferably, the organic solvent of the pyromellitic trimethylsilyl chloride that contains a certain amount of additive described in above-mentioned preparation methodThe modulator approach of solution is first quantitative pyromellitic trimethylsilyl chloride to be joined in organic solvent to use heating or ultrasonic agitationIt is fully dissolved and be modulated into quantitative pyromellitic trimethylsilyl chloride organic solvent solution; The additive that then adds use ultrasonic orAdd the organic solvent solution of the pyromellitic trimethylsilyl chloride that the abundant hybrid modulation of thermal agitation becomes to contain a certain amount of additive.
As preferably, in above-mentioned preparation method, described method specifically comprises the following steps:
(A) the nonwoven support layer material that is coated with porous polysulfone material is infiltrated to contain be with one or more hydroxylsOrganic acid or the m-phenylene diamine (MPD) aqueous solution of the buffer salt system that forms of its hydrate and organic base;
(B) use nitrogen air knife to remove porous polysulfone material surface and be with one or many with containing of nonwoven surface surplusThe m-phenylene diamine (MPD) aqueous solution of the buffer salt system that the organic acid of individual hydroxyl or its hydrate and organic base form, poly-in porousSulfone support layer material surface forms aqueous layer;
(C) by molten the organic solvent of described aqueous layer and the described pyromellitic trimethylsilyl chloride that contains a certain amount of additiveLiquid contact, by interfacial polymerization, at described porous polysulfone material Surface Creation aramid layer, is used nitrogen air knife to blow downSurplus organic solvent solution;
(D) by the product of baking oven post processing drying steps (C);
(E) by 25 DEG C of pure water rinsings;
(F), after the aqueous slkali neutralisation treatment that is 11-13 by 25 DEG C, pH, prepare polyamide reverse osmose membrane.
In step (E) with after the aqueous slkali neutralisation treatment that is 11-13 by 25 DEG C of pure water rinsings, pH (F), its nonwovenIn cloth, polysulfones support membrane, polyamide composite film, unreacted residues amine monomers content summation is less than 100ppm. Described pH is 11-13 aqueous slkali be one or two or more kinds in NaOH, sodium carbonate, sodium phosphate or sodium hydrogen phosphate be combined to form moltenLiquid.
As preferably, the polyamide reverse osmose membrane form described in above-mentioned preparation method is flat sheet membrane, hollow-fibre membrane.
In the present invention, the too small or excessive formation to composite membrane on it of membrane aperture has a significant impact, the too small harm of membrane apertureHinder the abundant immersion of aqueous phase solution, the polyamide composite film effectively generating in sorting hole is crossed and is thinly easily caused defect, and because of top layerThe excessive permeant flux of polyamide thickness is also less. The membrane aperture interior polyamide generating of effective sorting hole that easily causes bigger than normal is compoundThe blocked up permeant flux that affects of film, the excessive polyamide composite film overall structure generating on it of membrane aperture easily causes defect.
Use deionized water rinsing face, and use nitrogen air knife purging diaphragm to be stained with liquid stay. The configuration of aqueous phase solution: firstThe organic acid or its hydrate that contain with one or more hydroxyls are joined in pure water, it is fully dissolved and be modulated into pH and be1.9-2.5 between acid solution; Then adding the abundant hybrid modulation of corresponding organic base to become pH is that buffering between 2.0-6.0 is moltenLiquid, finally adding the abundant hybrid modulation of m-phenylene diamine (MPD) to become pH is organic with one or more hydroxyls contained between 4.5-7.2The m-phenylene diamine (MPD) aqueous solution of the buffer salt system that acid or its hydrate and organic base form. Porous polysulfone supporting layer material is soakedBe less than above-mentioned aqueous phase solution, after 0.5-1min, remove solution, use nitrogen air knife to purge porous polysulfone supporting layer side and nonwovenTop layer side residual water solution, to dry, forms aqueous layer at porous polysulfone supporting layer material surface. Organic solvent solutionConfiguration: be first that pyromellitic trimethylsilyl chloride between 0.05-3.0% joins in organic solvent by mass percent concentration, use addsHeat or ultrasonic agitation are fully dissolved it and are modulated into quantitative pyromellitic trimethylsilyl chloride organic solvent solution; Then add quality hundredPoint specific concentration is that the additive between 0.005-2% uses ultrasonic or adds the abundant hybrid modulation of thermal agitation and become to contain a certain amount of interpolationThe organic solvent solution of the pyromellitic trimethylsilyl chloride of agent. Use dispense tip by this organic solvent solution be coated on uniformly contain water-solubleOn the porous polysulfone supporting layer material surface of liquid layer, after interface polymerization reaction 20-50s, nitrogen air knife purges film surface and removesExcessive organic solvent solution, heat treatment 3-6min at 80-95 DEG C, at porous polysulfone material Surface Creation aramid layer.
The porous polysulfone material that aramid layer is contained on the surface that step 1 is obtained is by 25 DEG C of pure water rinsings, then logicalAfter the aqueous slkali neutralisation treatment that to cross 25 DEG C, pH be 11-13, obtain unreacted in nonwoven, polysulfones support membrane, polyamide composite filmResidual amine content of monomer summation is less than the polyamide reverse osmose membrane of 100ppm.
Beneficial effect
Rinsing treatment process gentleness required for the present invention, simple, efficient, in rinsing caudacoria, the residual total amount of unreacted amine is low,Easily realize the polyamide reverse osmose membrane preparation method that industrialization is prepared continuously fast. The polyamide reverse osmose membrane preparing existsUnder 800psi, 25 DEG C, 1GPM, 32000ppmNaCl simulated seawater solution testing condition, NaCl removal efficiency >=99.8%, produces water logicalAmount >=35GPM, possesses equipment with high desalinization, high yield water flux performance.
Brief description of the drawings
Fig. 1 is for having shown preparation technology's flow chart of the present invention
The surface structure of the porous polysulfones support membrane that Fig. 2 uses by electron-microscopic analysis comparative example 1
The surface structure of the porous polysulfones support membrane that Fig. 3 uses by electron-microscopic analysis comparative example 2
The surface structure of the porous polysulfones support membrane that Fig. 4 uses by electron-microscopic analysis comparative example 3
Fig. 5 is by the surface structure of electron-microscopic analysis embodiment 1 polyamide reverse osmose membrane
Fig. 6 is embodiment 1-11 unreacted residues amine macroanalysis result schematic diagram in film under different rinsing conditions
Wherein: zero refers to 25 DEG C of pure water rinsing 4min, the NaOH aqueous solution neutralisation treatment of 25 DEG C of mass percents 1%2min；
● refer to 25 DEG C of pure water rinsing 2min, the NaOH aqueous solution neutralisation treatment 2min of 25 DEG C of mass percents 1%;
■ refers to 25 DEG C of pure water rinsing 4min
Detailed description of the invention
Below enforcement of the present invention is illustrated:
Comparative example 1
Use surface apertures average value ranges between 40-50nm, deviate is under 1.52,0.1MPa test pressure, itsPure water flux is 312L/m2The porous polysulfones support membrane of/h. Use deionized water rinsing face, and use nitrogen air knife to purgeDiaphragm is stained with liquid stay. The configuration of aqueous phase solution: the citric acid that is first 3.2% by mass percent concentration joins in pure water, makesIt fully dissolves, and to be modulated into pH be 2.0 acid solution; Then add the abundant hybrid modulation of 10ml/L triethylamine become pH be 3.1 slowDissolved liquid, finally adding the abundant hybrid modulation of m-phenylene diamine (MPD) of mass percent concentration 4.8% to become pH is 5.2 m-phenylene diamine (MPD) waterSolution. Porous polysulfone supporting layer material is immersed into above-mentioned aqueous phase solution, after 0.5min, removes solution, use nitrogen air knife to blowSweep porous polysulfone supporting layer side and nonwoven top layer side residual water solution to dry, porous polysulfone supporting layer material surface shapeBecome aqueous layer. The configuration of organic solvent solution: the pyromellitic trimethylsilyl chloride that is first 0.1% by mass percent concentration joinsIn isoparG organic solvent, use heating or ultrasonic agitation that it is fully dissolved and be modulated into quantitative pyromellitic trimethylsilyl chloride and haveMachine solvent solution; Then adding mass percent concentration is 0.07% tbp, uses ultrasonic or to add thermal agitation fully mixedClose and be modulated into organic solvent solution. Use dispense tip this organic solvent solution to be coated on uniformly to the porous that contains aqueous layerProperty polysulfone supporting layer material surface on, after interface polymerization reaction 30s, use nitrogen air knife to blow down the excessive organic solvent in film surface moltenLiquid, heat treatment 3min at 95 DEG C, at porous polysulfone material Surface Creation aramid layer.
The porous polysulfone material that aramid layer is contained on the surface obtaining is by 25 DEG C of pure water tank rinsing 4min, then logicalThe sodium hydrate aqueous solution neutralisation treatment 2min that to cross 25 DEG C, mass percent concentration be 1%, obtains polyamide reverse osmose membrane.
Comparative example 2
Except using surface apertures average value ranges between 5-15nm, deviate is under 1.72,0.1MPa test pressure, itsPure water flux is 154L/m2/ h porous polysulfones support membrane outside, all the other steps are identical with comparative example 1.
Embodiment 1
Except using surface apertures average value ranges between 10-30nm, deviate is that 1.68,20-25nm hole number is 480Individual/um2, its pure water flux is 209L/m2Outside the porous polysulfones support membrane of/h, all the other steps are identical with comparative example 1.
Embodiment 2
Except m-phenylene diamine (MPD) mass percent concentration is that to become pH be 4.99 the m-phenylene diamine (MPD) aqueous solution to 3.0 abundant hybrid modulationOutward, all the other steps are identical with embodiment 1.
Embodiment 3
Except m-phenylene diamine (MPD) mass percent concentration is that to become pH be 5.12 the m-phenylene diamine (MPD) aqueous solution to 4.0 abundant hybrid modulationOutward, all the other steps are identical with embodiment 1.
Embodiment 4
Except m-phenylene diamine (MPD) mass percent concentration is that to become pH be 5.12 the m-phenylene diamine (MPD) aqueous solution to 5.0 abundant hybrid modulationOutward, all the other steps are identical with embodiment 1.
Embodiment 5
Except triethylamine addition be the abundant hybrid modulation of 20ml/L to become pH be 3.8 cushioning liquid, finally add quality hundredIt is outside 5.45 the m-phenylene diamine (MPD) aqueous solution that the abundant hybrid modulation of m-phenylene diamine (MPD) that point specific concentration is 4.8% becomes pH, all the other steps withEmbodiment 1 is identical.
Embodiment 6
Except triethylamine addition be the abundant hybrid modulation of 30ml/L to become pH be 4.4 cushioning liquid, finally add quality hundredIt is outside 5.7 the m-phenylene diamine (MPD) aqueous solution that the abundant hybrid modulation of m-phenylene diamine (MPD) that point specific concentration is 4.8% becomes pH, all the other steps and realityExecute example 1 identical.
Embodiment 7
Except triethylamine addition be the abundant hybrid modulation of 40ml/L to become pH be 4.9 cushioning liquid, finally add quality hundredIt is outside 5.9 the m-phenylene diamine (MPD) aqueous solution that the abundant hybrid modulation of m-phenylene diamine (MPD) that point specific concentration is 4.8% becomes pH, all the other steps and realityExecute example 1 identical.
Embodiment 8
Except triethylamine addition be the abundant hybrid modulation of 50ml/L to become pH be 5.5 cushioning liquid, finally add quality hundredIt is outside 6.2 the m-phenylene diamine (MPD) aqueous solution that the abundant hybrid modulation of m-phenylene diamine (MPD) that point specific concentration is 4.8% becomes pH, all the other steps and realityExecute example 1 identical.
Embodiment 9
Except the additive in organic solvent solution is acetone, it adds mass percent concentration is outside 0.1%, all the other stepsIdentical with embodiment 6.
Embodiment 10
Except the additive in organic solvent solution is ferric acetyl acetonade, it adds mass percent concentration is outside 0.1%, itsRemaining step is identical with embodiment 6.
Embodiment 11
Except the additive in organic solvent solution is nickel acetylacetonate, it adds mass percent concentration is outside 0.1%, itsRemaining step is identical with embodiment 6.
Test the assessment of 1 film properties
The desalination of the polyamide reverse osmose membrane precompressed that test is prepared according to comparative example 1-2 and embodiment 1-11 after 1 hourRate and permeant flux. Precompressed 1 under 25 DEG C, the NaCl aqueous solution water inlet test condition of the flow velocity of 800psi, 1GPM, 32000ppmSalt rejection rate and permeant flux to film after hour are measured. Be HWTT-six pond high-pressure membranes for assessment of the device of reverse osmosis membraneBuilt-in testing platform (Hangzhou Water Treatment Technology Research and Development Center Co.ltd's self-control), comprising test pool, high-pressure pump, Yuan ShuiTank, pressure sensor, heat exchanger, effective film area is 26.5cm2. By comparative example 1-3 and prepared the gathering of embodiment 1-11After acid amides reverse osmosis membrane is arranged on test pool, use the NaCl aqueous solution of 32000ppm to carry out precompressed in 1 hour, then measure 20Minute the product water water yield, by with the former water of conductivity meter analysis to measure, produce the salinity of water and calculate salt rejection rate. Test resultAs table 1 and table 2
Table 1
| Classification | Salt rejection rate % | Permeant flux (GFD) |
| Embodiment 1 | 99.50％ | 29.57 |
| Embodiment 2 | 99.33％ | 33.05 |
| Embodiment 3 | 99.41％ | 30.05 |
| Embodiment 4 | 99.81％ | 32.05 |
| Embodiment 5 | 99.85％ | 31.05 |
| Embodiment 6 | 99.87％ | 32.05 |
| Embodiment 7 | 99.85％ | 36.05 |
| Embodiment 8 | 99.84％ | 34.05 |
| Embodiment 9 | 99.72％ | 37.05 |
| Embodiment 10 | 99.37％ | 40.17 |
| Embodiment 11 | 99.85％ | 38.73 |
| Comparative example 1 | 99.41％ | 25.68 |
| Comparative example 2 | 98.5％ | 20.3 |
The assessment of the residual total amount of unreacted amine in experiment-2 films
Comparative example 3
Use surface apertures average value ranges between 10-30nm, deviate is that 1.68,20-25nm hole number is 480Individual/um2, under 0.1MPa test pressure, its pure water flux is 209L/m2The porous polysulfones support membrane of/h. The punching of use deionized waterWash face, and use nitrogen air knife purging diaphragm to be stained with liquid stay. The configuration of aqueous phase solution: by mass percent concentration be first2.0% camphorsulfonic acid joins and in pure water, is modulated into pH and is 1.3 acid solution, then adds 12ml/L triethylamine fully to mixBe modulated into pH and be 8.9 cushioning liquid, finally add the abundant hybrid modulation of m-phenylene diamine (MPD) of mass percent concentration 4.8% to become pHBe 9.3 the m-phenylene diamine (MPD) aqueous solution. Porous polysulfone supporting layer material is immersed into above-mentioned aqueous phase solution, after 0.5min, removes moltenLiquid, uses nitrogen air knife to purge porous polysulfone supporting layer side and nonwoven top layer side residual water solution is extremely dry, poly-in porousSulfone support layer material surface forms aqueous layer. The configuration of organic solvent solution: what be first 0.1% by mass percent concentration is equalBenzene three formyl chlorides join in isoparG organic solvent, use heating or ultrasonic agitation make its fully dissolve be modulated into quantitativelyPyromellitic trimethylsilyl chloride organic solvent solution; Then adding mass percent concentration is 0.07% tbp, uses ultrasonicOr add the abundant hybrid modulation of thermal agitation and become organic solvent solution. Use dispense tip that this organic solvent solution is coated on and is contained uniformlyHave on the porous polysulfone supporting layer material surface of aqueous layer, after interface polymerization reaction 30s, use nitrogen air knife to blow down film tableThe excessive organic solvent solution of face, heat treatment 3min at 95 DEG C, at porous polysulfone material Surface Creation aramid layer.
The porous polysulfone material that aramid layer is contained on the surface obtaining is by 25 DEG C of pure water tank rinsing 4min, then logicalThe sodium hydrate aqueous solution neutralisation treatment 2min that to cross 25 DEG C, mass percent concentration be 1%, obtains polyamide reverse osmose membrane.
Assessment is according to the unreacted residues amine in comparative example 3 and the prepared polyamide reverse osmose membrane of embodiment 1-11Content carries out. Service property (quality) percent concentration is under 50% ethanol water 200ml, temperature 50 C condition, extracts above-mentioned poly-Acid amides reverse osmosis membrane, extraction time is 72 hours, the polyamide reverse osmose membrane sheet area of sampling is 1.5cm × 1.5cm, usesAmine content in ultraviolet specrophotometer analytical extraction liquid, obtains the content of unreacted residues amine in polyamide reverse osmose membrane.
Embodiment 12-22
Except 25 DEG C of pure water rinsing times are 2 minutes, all the other steps are corresponding identical with embodiment 1-11 respectively.
Embodiment 23-33
Except the sodium hydrate aqueous solution neutralisation treatment that is 1% without mass percent concentration, all the other steps and enforcementExample 1-11 correspondence is identical
Table 2
| Classification | Residual amine content (ppm) |
| Embodiment 1 | 85 |
| Embodiment 2 | 83 |
| Embodiment 3 | 74 |
| Embodiment 4 | 86 |
| Embodiment 5 | 91 |
| Embodiment 6 | 91 |
| Embodiment 7 | 77 |
| Embodiment 8 | 93 |
| Embodiment 9 | 74 |
| Embodiment 10 | 73 |
| Embodiment 11 | 74 |
| Embodiment 12 | 127 |
| Embodiment 13 | 113 |
| Embodiment 14 | 105 |
| Embodiment 15 | 140 |
| Embodiment 16 | 157 |
| Embodiment 17 | 162 |
| Embodiment 18 | 112 |
| Embodiment 19 | 181 |
| Embodiment 20 | 110 |
| Embodiment 21 | 117 |
| Embodiment 22 | 113 |
| Embodiment 23 | 97 |
| Embodiment 24 | 94 |
| Embodiment 25 | 89 |
| Embodiment 26 | 97 |
| Embodiment 27 | 105 |
| Embodiment 28 | 100 |
| Embodiment 29 | 86 |
| Embodiment 30 | 105 |
| Embodiment 31 | 89 |
| Embodiment 32 | 89 |
| Embodiment 33 | 86 |
| Comparative example 3 | 217.4 |
Claims (10)
1. a preparation method for polyamide reverse osmose membrane, is characterized in that, compound one deck merit on porous polysulfones support membraneThe fine and close composite bed of energy property;
Described functional fine and close composite bed is contained organic acid or its hydrate with one or more hydroxyls and had by useThe m-phenylene diamine (MPD) aqueous solution of the buffer salt system that machine alkali forms, organic with the pyromellitic trimethylsilyl chloride that contains a certain amount of additiveSolvent solution forms in the surface polycondensation of porous polysulfones support membrane;
Additive wherein refers to tbp, triphenylphosphine, aluminium isopropoxide, acetone, acetylacetone,2,4-pentanedione, aluminium acetylacetonate, secondOne or more in acyl acetone nickel, acetylacetone,2,4-pentanedione ruthenium (III), ferric acetyl acetonade, chromium acetylacetonate or acetylacetone,2,4-pentanedione gallium withOn combination, the mass percent of additive in pyromellitic trimethylsilyl chloride is 0.005-2%; Pyromellitic trimethylsilyl chloride is organic moltenMass percent in agent solution is 0.05-3.0%;
Described buffer salt system is the mixed solution with the organic acid of one or more hydroxyls or its hydrate and organic base;
Wherein, the organic acid with one or more hydroxyls adopting is lactic acid, D-malic acid, L MALIC ACID, DL-appleA kind of or two kinds of above combinations in tartaric acid, citric acid, tartaric acid; The organic base adopting be triethylamine, trimethylamine orThe combination of one or two or more kinds in diethylamine;
The organic solvent adopting is one in isoparM, isoparH, isoparL, isoparE, isoparG or n-hexaneKind or two kinds of above combinations;
Described porous polysulfones support membrane surface apertures mean value between 10-30nm, deviate≤1.8; Porous is poly-The hole count of sulfone support membrane surface unit area is at 200-600/um2Between, and porous polysulfones support membrane existsUnder 0.1MPa test pressure, its pure water flux is 100-300L/m2Between/h;
The mass percent of the described organic acid with one or more hydroxyls in the m-phenylene diamine (MPD) aqueous solution is 0.1-5%；
The mass percent of described organic base in the m-phenylene diamine (MPD) aqueous solution is 0.1-5%;
The mass percent of the m-phenylene diamine (MPD) in the described m-phenylene diamine (MPD) aqueous solution is 0.1-7%.
2. a kind of preparation method according to claim 1, is characterized in that, described porous polysulfones support membrane surfaceAperture mean value between 20-25nm, deviate≤1.3; The hole count of porous polysulfones support membrane surface unit area exists400-500/um2Between; And porous polysulfones support membrane is under 0.1MPa test pressure, and its pure water flux is 200-250L/m2Between/h, porous polysulfones support membrane and nonwoven stack thickness are that between 120-170um, polyamide reverse osmosis is multipleClosing layer thickness is between 80-250nm.
3. a kind of preparation method according to claim 1, is characterized in that, described with one or more hydroxylsThe mass percent of organic acid in the m-phenylene diamine (MPD) aqueous solution is 1.5-2.5%.
4. a kind of preparation method according to claim 1, is characterized in that, described organic base is water-soluble at m-phenylene diamine (MPD)Mass percent in liquid is 1.1-1.5%.
5. a kind of preparation method according to claim 1, is characterized in that, one or more hydroxyls are with in described containingOrganic acid or the modulator approach of the m-phenylene diamine (MPD) aqueous solution of the buffer salt system that forms of its hydrate and organic base be first willThe organic acid or its hydrate that contain with one or more hydroxyls join in pure water, it is fully dissolved and be modulated into pH and be1.9-2.5 between acid solution; Then adding the abundant hybrid modulation of corresponding organic base to become pH is delaying between 2.0-6.0Dissolved liquid, finally adds the abundant hybrid modulation of m-phenylene diamine (MPD) to become pH to contain with one or more hydroxyls between 4.5-7.2The m-phenylene diamine (MPD) aqueous solution of the buffer salt system that organic acid or its hydrate and organic base form.
6. a kind of preparation method according to claim 1, is characterized in that, described contain a certain amount of additive allThe modulator approach of the organic solvent solution of benzene three formyl chlorides is first quantitative pyromellitic trimethylsilyl chloride to be joined to organic solventIn, use heating or ultrasonic agitation that it is fully dissolved and be modulated into quantitative pyromellitic trimethylsilyl chloride organic solvent solution; ThenThe additive that adds uses ultrasonic or adds pyromellitic trimethylsilyl chloride that the abundant hybrid modulation of thermal agitation becomes to contain a certain amount of additiveOrganic solvent solution.
7. a kind of preparation method according to claim 1, is characterized in that, described method comprises the following steps:
(A) the nonwoven support layer material that is coated with porous polysulfone material is infiltrated and contain with one or more hydroxylsThe m-phenylene diamine (MPD) aqueous solution of the buffer salt system that organic acid or its hydrate and organic base form;
(B) using nitrogen air knife to remove porous polysulfone material surface is with one or more with containing of nonwoven surface surplusThe m-phenylene diamine (MPD) aqueous solution of the buffer salt system that the organic acid of hydroxyl or its hydrate and organic base form, at porous polysulfonesSupport membrane material surface forms aqueous layer;
(C) by the organic solvent solution of described aqueous layer and the described pyromellitic trimethylsilyl chloride that contains a certain amount of additiveContact, by interfacial polymerization, at described porous polysulfone material Surface Creation aramid layer, is used nitrogen air knife to blow down superfluousOrganic solvent solution;
(D) by the product of baking oven post processing drying steps (C);
(E) by 25 DEG C of pure water rinsings;
(F), after the aqueous slkali neutralisation treatment that is 11-13 by 25 DEG C, pH, prepare polyamide reverse osmose membrane.
8. a kind of preparation method according to claim 7, is characterized in that, passes through in step (E) with (F)After the aqueous slkali neutralisation treatment that 25 DEG C of pure water rinsings, pH are 11-13, its nonwoven, polysulfones support membrane, polyamide composite filmInterior unreacted residues amine monomers content summation is less than 100ppm.
9. a kind of preparation method according to claim 7, is characterized in that, the alkali that described pH is 11-13 is moltenLiquid is one or two or more kinds solution being combined to form in NaOH, sodium carbonate, sodium phosphate or sodium hydrogen phosphate.
10. a kind of preparation method according to claim 1, is characterized in that, described polyamide reverse osmose membrane formFor flat sheet membrane, hollow-fibre membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766709.2A CN104474926B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of polyamide reverse osmose membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766709.2A CN104474926B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of polyamide reverse osmose membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104474926A CN104474926A (en) | 2015-04-01 |
| CN104474926B true CN104474926B (en) | 2016-05-04 |
Family
ID=52749611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410766709.2A Active CN104474926B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of polyamide reverse osmose membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104474926B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597574B (en) * | 2016-02-03 | 2018-02-23 | 东华大学 | A kind of preparation method of compound forward osmosis membrane |
| CN106370548B (en) * | 2016-09-21 | 2018-08-31 | 西安建筑科技大学 | A kind of preparation method of the polyamide quartz crystal chip of polyelectrolyte assembly |
| CN106370549B (en) * | 2016-09-21 | 2019-01-11 | 西安建筑科技大学 | A kind of preparation of sulfone quasi polymer quartz crystal chip and recycling method |
| CN106512731A (en) * | 2016-12-06 | 2017-03-22 | 苏州富艾姆工业设备有限公司 | Preparation method of reverse osmosis membrane for pipeline direct drinking water system |
| CN106552515A (en) * | 2016-12-06 | 2017-04-05 | 苏州富艾姆工业设备有限公司 | A kind of preparation method of high-performance reverse osmosis membrane |
| CN106512733A (en) * | 2016-12-12 | 2017-03-22 | 苏州富艾姆工业设备有限公司 | Preparation method of anti-pollution reverse osmosis membrane |
| CN106512732A (en) * | 2016-12-12 | 2017-03-22 | 苏州富艾姆工业设备有限公司 | Preparation method of ultrathin reverse osmosis membrane |
| CN106925132B (en) * | 2017-04-19 | 2020-02-07 | 青岛天兰环境股份有限公司 | Reverse osmosis membrane repairing agent and repairing method |
| CN107376667B (en) * | 2017-08-25 | 2020-11-27 | 上海城市水资源开发利用国家工程中心有限公司 | Method and device for preparing nano-filtration/forward-osmosis amphibious-performance CTA (CTA) membrane |
| CN109632678A (en) * | 2018-11-16 | 2019-04-16 | 蓝星（杭州）膜工业有限公司 | A kind of detection method of polyamide composite film piece residual amine content |
| CN109603587A (en) * | 2018-11-16 | 2019-04-12 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane |
| CN109647200A (en) * | 2018-12-21 | 2019-04-19 | 天津膜天膜科技股份有限公司 | The method of high flash solvent continuous production External Pressure Type hollow fiber nanofiltration membrane |
| CN110052169B (en) * | 2019-04-25 | 2021-03-16 | 武汉大学 | Method for modifying composite reverse osmosis membrane by magnetic carbon nano tube |
| CN110813107A (en) * | 2019-11-08 | 2020-02-21 | 恩泰环保科技（常州）有限公司 | High-flux low-pressure composite reverse osmosis membrane and preparation method thereof |
| CN110975621B (en) * | 2019-12-25 | 2022-05-03 | 恩泰环保科技（常州）有限公司 | Reverse osmosis membrane based on weak base-weak acid buffer system and preparation method thereof |
| CN111112030A (en) * | 2019-12-31 | 2020-05-08 | 苏州普希环保科技有限公司 | Multilayer film and method for producing same |
| CN111450714A (en) * | 2020-04-17 | 2020-07-28 | 蓝星（杭州）膜工业有限公司 | Method for preparing composite nanofiltration membrane by using multi-element buffer system |
| CN114053885B (en) * | 2020-07-30 | 2024-06-25 | 万华化学集团股份有限公司 | High-pressure-resistant polyamide membrane and preparation method thereof |
| CN112007525A (en) * | 2020-08-07 | 2020-12-01 | 浙江机电职业技术学院 | Preparation method of high-performance salt-separating nanofiltration membrane |
| CN111905577A (en) * | 2020-08-12 | 2020-11-10 | 浙江奥氏环境科技有限公司 | Method for reducing content of residual amine of reverse osmosis membrane |
| CN113461933B (en) * | 2021-06-01 | 2022-09-06 | 浙江大学 | Polymer self-supporting nano film, continuous and macro preparation method and application thereof |
| CN115228290A (en) * | 2022-08-03 | 2022-10-25 | 万华化学集团股份有限公司 | Preparation method of cleaning-resistant reverse osmosis membrane |
| CN117065575B (en) * | 2023-10-16 | 2024-01-30 | 蓝星（杭州）膜工业有限公司 | Nanofiltration membrane and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030022915A (en) * | 2001-09-11 | 2003-03-19 | 주식회사 새 한 | Producing method of composite polyamide reverse osmosis membrane |
| KR100716210B1 (en) * | 2005-09-20 | 2007-05-10 | 웅진코웨이주식회사 | Preparation method of polyamide reverse osmosis composite membrane and polyamide reverse osmosis composite membrane prepared therefrom |
| CN102133507A (en) * | 2011-02-28 | 2011-07-27 | 浙江理工大学 | High-desalination reverse osmosis composite membrane |
| CN103143271A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院长春应用化学研究所 | Reverse osmosis complex membrane and preparation method thereof |
-
2014
- 2014-12-12 CN CN201410766709.2A patent/CN104474926B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104474926A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104474926B (en) | A kind of preparation method of polyamide reverse osmose membrane | |
| Suwaileh et al. | Forward osmosis membranes and processes: A comprehensive review of research trends and future outlook | |
| Qasim et al. | Water desalination by forward (direct) osmosis phenomenon: A comprehensive review | |
| Qiu et al. | Synthesis of high flux forward osmosis membranes by chemically crosslinked layer-by-layer polyelectrolytes | |
| Arena et al. | Surface modification of thin film composite membrane support layers with polydopamine: Enabling use of reverse osmosis membranes in pressure retarded osmosis | |
| Zhong et al. | Development of thin-film composite forward osmosis hollow fiber membranes using direct sulfonated polyphenylenesulfone (sPPSU) as membrane substrates | |
| She et al. | Osmotic power production from salinity gradient resource by pressure retarded osmosis: Effects of operating conditions and reverse solute diffusion | |
| Emadzadeh et al. | Synthesis of thin film nanocomposite forward osmosis membrane with enhancement in water flux without sacrificing salt rejection | |
| Liu et al. | Double-blade casting technique for optimizing substrate membrane in thin-film composite forward osmosis membrane fabrication | |
| Klaysom et al. | Forward and pressure retarded osmosis: potential solutions for global challenges in energy and water supply | |
| CN104209022A (en) | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof | |
| Ong et al. | Novel cellulose esters for forward osmosis membranes | |
| Boricha et al. | Acrylonitrile butadiene styrene/chitosan blend membranes: Preparation, characterization and performance for the separation of heavy metals | |
| Saraf et al. | Poly (vinyl) alcohol coating of the support layer of reverse osmosis membranes to enhance performance in forward osmosis | |
| CN108187511A (en) | High flux and high retention ratio polyamide composite reverse osmosis membrane and preparation method thereof | |
| Zhao et al. | Influence of different ion types and membrane orientations on the forward osmosis performance | |
| CN103537200A (en) | Cellulose acetate forward osmotic membrane and preparation method thereof | |
| JP2014521499A (en) | Polyamide-based reverse osmosis separation membrane excellent in initial permeate flow rate and method for producing the same | |
| AU2018274846B2 (en) | Polyaniline membranes formed by phase inversion for forward osmosis applications | |
| Yang et al. | Fabrication of thin-film composite hollow fiber membranes in modules for concentrating pharmaceuticals and separating sulphate from high salinity brine in the chlor-alkali process | |
| Sun et al. | Development of high-flux and robust reinforced aliphatic polyketone thin-film composite membranes for osmotic power generation: Role of reinforcing materials | |
| Baig et al. | Enhancing the separation performance of aqueous phase separation-based membranes through polyelectrolyte multilayer coatings and interfacial polymerization | |
| Fu et al. | Study on high-performance pervaporation desalination membranes prepared by interfacial reactions between two aqueous monomers | |
| KR101517653B1 (en) | High Flux Reverse Osmosis Membrane Comprising Xanthene Compound And Manufacturing Method Thereof | |
| Elewa et al. | Effect of cell hydrodynamics in desalination of saline water by sweeping air pervaporation technique using innovated membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |